Glutamic acid polymer adherents

ABSTRACT

A LEATHER-LIKE COMPOSITE COMPRISING A COATING ADHESIVELY SECURED TO A SUBSTRATE, SAID COATING COMPRISING A MAJOR AMOUNT OF A POLYGLUTAMIC ACID AND AN ADHESIVE CONTAINING A DIISOCYANATO-SUBSTITUTED ALIPHATIC CARBOXYLIC ACID ESTER AS HE PRINCIPAL CONSTITUENT. THE ADHESIVE USED IN THE PRESENT INVENTION PROVIDES A GOOD BOND BETWEEN THE POLYMERIC FILM AND THE SUBSTRATE SURFACE, FOR EXAMPLE, A COTTON CLOTH. THE COMPOSITE EXHIBITS AN IMPROVED LUSTER AND EXCELLENT RESISTANCE TO LIGHT, AS WELL AS AN ENHANCED ELONGATION.

3,729,366 GLUTAMIC ACID POLYMER ADHERENTS Yasuo Fujimoto, Machida,Koichi Nagaoka, Tokyo, and Keizo Tatsukawa, Machida, Japan, assignors toKyowa Hakko Kogyo Co., Ltd., Tokyo, Japan No Drawing.Continuation-impart of application Ser. No.

776,809, Nov. 18, 1968, and now abandoned. This application Jan. 15,1971, Ser. No. 106,930

Claims priority, application Japan, Nov. 22, 1967, 42/ 74,709 Int. Cl.B32b 27/02, 27/34 U.S. Cl. 161-89 20 Claims ABSTRACT OF THE DISCLOSUREThis is a continuation-in-part of pending application Ser. No. 776,809,filed Nov. 18, 1968, and now abandoned.

BACKGROUND OF THE INVENTION The present invention relates to improvedpolymer adherents consisting of polymers (homoor co-polymer or blendpolymer) of glutamic acid-' -esters with or without other amino acids.More particularly, the present invention is directed to compositecomprising a coating which has an improved luster and light resistancewhich is provided with an improved adhesive which secures said coatingto a substrate in an elfective manner.

It is well known that a polymeric material consisting of a major amountof a polymer (homoor co-polymer or blend polymer) of a glutamicacid-'y-ester with or with out another amino acid (hereinafter referredto merely as polyglutamic acid) is an excellent synthetic resinousmaterial and can be used as synthetic fibers or films. Thus, because ofits chemical nature it has properties between Wool and silk and, infact, has characteristics and feel which resemble those of naturalleather.

However, in utilizing the film-forming property of polyglutamic acid inproducing polyglutamic acid adherents, the following problems have beenencountered:

(1) There is a problem of providing sufiicient adhesion between thepolyglutamic acid film and the surface of substrate to be coated.

(2) Polyglutamic acid film is poor in its luster qualities.

(3) Polyglutamic acid film is low in its elongation.

An object of the present invention is to provide an improved compositeof a polyglutamic acid film adhered to a substrate.

Another object of the present invention is to provide an adhesivematerial which produces an effective adhesion between the polyglutamicacid film and the substrate to be coated.

A further object of the present invention is to provide a polyglutamicacid film which possesses good luster and light resistance propertiesand an improved elongation.

Other objects and further scope of applicability of the presentinvention will become apparent from the detailed description givenherein after; it should be understood, however, that the detaileddescription and specific examples, whileindicating preferred embodimentsof the United States Patent 3,729,366 Patented Apr. 24, 1973 presentinvention, are given by way of illustration only, since various changesand modifications within the spirit and scope of the invention willbecome apparent to those skilled in the art from this detaileddescription.

Pursuant to the present invention, it has been found that theabove-mentioned disadvantages may be eliminated and a much improvedcomposite containing a polyglutamic acid film may be obtained by using aurethane resin as an adhesive for adhering the polyglutamic acid coatingor film to the desired substrate. According to the present invention, ithas been found that a urethane resin comprising as its principalconstituent a diisocyanate sub stituted alkanoic acid ester having thefollowing formula:

wherein R can be, either unsaturated or saturated, alkyl, alkoxyalkyl,cycloalkyl, aryl, alkaryl or aralkyl, either unsubstituted orsubstituted with halogen, nitro, alkoxy, carboalkoxy, acylamino,dialkylamiuo, carboalkoxyarnino (alkoxycarbonylamino) orcarboaralkoxyarnino (aralkoxycarbonylamino) radicals, R is alkylene oralkylidene, R is hydrogen or a radical having the following formula:

wherein Y can be, either unsaturated or saturated, alkyl, alkoxyalkyl,cycloalkyl, aryl, alkaryl or aralkyl, either unsubstituted orsubstituted with halogen, nitro, alkoxy, carboalkoxy, acylamino,dialkylamino, carboalkoxyamino (alkoxycarbonylamino) orcarboaralkoxyamino (aralkoxycarbonylamino) radicals, exhibits excellentcompatibility (co-dissolubility) with polyglutamic acid. It has beenfurther found that when using said urethane resin as an adhesive forpolyglutamic acid, not only is the adhesiveness referred to abovesubstantially improved but also, and unexpectedly, the luster of thepolyglutamic acid film is markedly enhanced. The ester of alkanoic aciddiisocyanate used as the adhesive in the present invention can beobtained by phosgenating an ester of the correspondinga,w-diaminoalkanoic acid.

According to the present invention it has been found that glutamic acidpolymer adherents, in which the abovementioned type of urethane resinsare used as adhesives, possess excellent light-resistance and thus it isconvenient to produce therefrom final products having light or paleshades such as a white color, a yellow color, and the like. Thus, in thecase of producing colored polyglutamic acid adherents (coatings orfilms), products having clear colors can be readily obtained.

In order to improve the elongation of the polyglutamic acid adherent, itis advantageous to add to said polyglutamic acid adherent a plasticizerwhich exhibits excellent compatibility with said polyglutamic acid.Suitable plasticizers include diesters of amino acids and derivativesthereof. Plasticizers which are compatible with polyglutamic acid arediscussed in U .S. patent application Ser. No. 761,853, filed Sept. 23,1968, and now abandoned.

As stated above, the particular urethane resins which are used as theadhesive for the glutamic acid polymer films according to the presentinvention are alkanoic acid diisocyanate esters. Although any of thecommercially available compounds can be used, the following compoundsare typical; the esters of 2,6-diisocyanato carproic acid (lysinediisocyanate), 2,4-diisocyanato butyric acid, 2,5-diisocyanato valericacid, 2,7-diisocyanato acid and 2, 8-diisocyanato caprylic acid such asthe methyl, ethyl, npropyl, i-propyl, n-butyl and isomers thereof,n-pentyl and isomers thereof, n-hexyl and isomers thereof, n-octyl andisomers thereof, n-decyl and isomers, n-dodecyl and isomers, stearyl,palmityl, methoxymethyl, ethoxymethyl, 2- methoxyethyl, Z-ethoxyethyl,2-propoxyethyl, Z-butoxyethyl, 3-methoxypropyl, 3-ethoxypropyl,4-methoxybutyl, 4ethoxybutyl, phenyl, benzyl, o-tolyl, p-tolyl,phenylethyl, p-tolylmethyl, o-tolylmethyl, o-(2-chlorotolyl), 2-chloroethyl, 2-br0moethyl, 2-chloropropyl, 3-chloropropyl,1,2-dichloropropyl, 2,3-dichloropropyl, cyclobutyl, cyclopentyl,cyclohexyl, cycloheptyl, cyclooctyl, cyclodecyl, cyclopentylmethyl,cyclohexylmethyl and cyclobutylmethyl esters; the homoor hetero-diestersof 2,4- diisocyanato glutaric acid, 2,5-diisocyanato adipic acid, 2,6-diisocyanato pimelic acid, 2,7-diisocyanato suberic acid and2,9-diisocyanato sebacic acid such as dimethyl, diethyl, dipropyl(di-n-propyl and di-i-propyl), dibutyl and isomers, dioctyl and isomers,didecyl and isomers, didodecyl, distearyl, diphenyl, dibenzyl,di(o-tolyl), di(p-tolyl), di(fl-phenylethyl), di(p-tolylmethyl) di[o (2chlorotolyl)], di(Z-chloroethyl), di(2-chloropropyl),di(2,3-dichloropropyl) di (methoxymethyl) di( Z-methoxyethyl) di(2-ethoxyethyl) di( 2-propoxyethyl) di (Z-butoxyethyl di(cyclohexyl), anddi(cyclopentyl) diesters and mixed esters such as methyl-ethyl,methyl-propyl, methyl-butyl, ethyl-propyl, ethyl-butyl,n-propyl-i-propyl, propylbutyl, phenyl-octyl, benzyl-stearyl, andmethyl-benzyl diesters. The diisocyanate may be either optically activeor inactive. The diisocyanates preferred for use are the alkyl esters of2,4 diisocyanato valeric acid and 2,6-diisocyanato caproic acid.

Typical of the ester group represented by the R and Y are; methyl, ethyln-propyl, i-propyl, n-butyl and isomers thereof, n-pentyl and isomersthereof, n-hexyl and isomers thereof, n-heptyl and isomers thereof,n-octyl and isomers thereof, n-decyl and isomers thereof, n-dodecyl(lauryl) and isomers thereof, cetyl, stearyl, oleyl, cyclobutyl,cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclobutylmethyl,cyclopentylmethyl, cyclohexylmethyl, cyclooctyl-methyl, methcyclohexyl,phenyl, o-tolyl, ptolyl, benzyl, li-phenylethyl, p-tolylmethyl,o-tolylrnethyl, o-(2-chlorotolyl), methoxymethyl, ethoxymethyl,2-nitroethyl, 2-chloroethyl, 2-bromoethyl, Z-fiuoroethyl, Z-cyanoethyl,2-chloropropyl, 3-chloropropyl, 1,2-dichloropropyl, 2,3-dichloropropyl,3-bromopropyl, vinyl, allyl, crotyl, pchlorobenzyl, p-bromobenzyl,p-fluorobenzyl, p-nitrobenzyl, p-cyanobenzyl, p-methoxybenzyl,o-carboethoxybenzyl, p carboethoxybenzyl, p carbomethoxybenzyl,pentachlorobenzyl, o-methoxybenzyl, or p-ethoxybenzyl, 0- orp-methoxyphenyl, p-chlorophenyl, p-nitrophenyl, pentachlorophenyl,p-carbomethoxyphenyl, p-(N-methylaminophenyl), p-(N-ethylaminophenyl), p(N,N dimethylaminophenyl) p-(N,N-diethylaminophenyl), p-(N-methyl-N-ethylaminophenyl) p- (N-methylaminobenzyl)p-(N-acetylaminophenyl), p-(N acetylaminobenzyl), p-(N-carbomethoxyaminophenyl), p (N carbomethoxyaminobenzyl),fi-(dimethylaminoethyl), ,B-(carboethoxyethyl), andp-(N-carbohenzoxyaminophenyl), Z-methoxyethyl, 2-ethoxyethyl,3-methoxypropyl, 3-ethoxypropyl, 3- butoxypropyl, 4-methoxybutyl,4-ethoxybutyl, and 2-butoxyethyl.

In preparing urethane resin adhesive containing the diisocyanatoalkanoic acid esters as the main ingredient thereof, the technique forpreparing urethane resin adhesites containing tolylenediisocyanate orhexamethylenediisocyanate can be effectively used with these compoundsas starting materials. The adhesive of the present invention can also beused as a moisture cured adhesive in the form of a one-component typeadhesive or a two-component urethane adhesive when used together with apolyol, a polyolypolyester, an acrylic-modified polyol, and the like. Inthe case of employing the adhesive as a two-component type adhesive, itis possible to prepare a soft, medium-hard and hard adhesive by merelyselecting the kind of polyols to be employed. The type of adhesiveutilized depends upon the particular uses to which it is to besubjected.

The surface of substrates to which the polyglutamic acid can be adheredaccording to the present invention include any substrates to which aurethane resin adhesive can be applied. Typical substrates include wovenfabrics and knitted fabrics made of polyamide fibers, polyester fibers,polyacrylonitrile fibers, polyvinyl chloride fibers, regenerated fiberssuch as viscose and acetate, natural fibers such as cotton, silk, linen,wool, and the like; fibrous substrates such as paper, non-woven fabrics,and textile mats, plate-like and sheet-like articles of varioussubstrates, the surfaces of which are coated with a synthetic resin suchas a polyamide resin (nylon 6 and the like), a polyurethane resin, apolyester resin (alkyd resin) and polyvinyl chloride, and plate-likearticles of wood 'or metals such as iron and aluminum. Cotton substratesare preferred.

Although the homoor co-polymers or blend polymers of any kind ofglutamic acid -esters with or without other amino acids or derivativesthereof which are commonly used in the field of amino acid or peptidechemistry, wherein the glutamic acid 'y-esters have the followingformulae:

COOR4 COOR OOO H2)2 o H2): Hz);

H-NH: H-NHz H-NH:

O O H O OH O O H including those which are either optically active oroptically inactive can be used as the film or adherent according to thepresent invention, it is more desirable to use the homoor copolymers orblend polymers wherein the glutamic acid 'y-ester or 'y-esters having anR or R group selected from the following residues are a major component:a monoor di-valent hydrocarbon residue consisting of a saturated orunsaturated aliphatic hydrocarbon residue having 1 to 20 carbons, asaturated or unsaturated cycloaliphatic hydrocarbon residue having 4 to20 carbons, an aromatic hydrocarbon residue having 6 to 20 carbonsincluding aryl, arylene, alkaryl, alkarylene, aralkyl, aralkenyl,aralkylene, and aralkenylene, and a residue belonging in theabove-mentioned types of hydrocarbons having a substituent orsubstituents selected from the group consisting of chloro, bromo,fluoro, nitro, cyano (nitrile), alkoxy, carboalkoxy, carboaryloxy,carboalkaryloxy, carboaralkoxy, monoand di-alkylated amino, acylatedamino, carboalkoxyamino and carboaralkoxyamino.

Typical of ester groups represented by R, are: methyl, ethyl, n-propyl,i-propyl, n-butyl and isomers thereof, n-pentyl and isomers thereof,n-hexyl and isomers thereof, n-heptyl and isomers thereof, n-octyl andisomers thereof, n-decyl and isomers thereof, n-dodecyl (lauryl) andisomers thereof, cetyl, stearyl, oleyl, cyclobutyl, cyclopentyl,cyclohexyl, cycloheptyl, cyclooctyl, cyclobutylmethyl,cyclopentylmethyl, cyclohexylmethyl, cyclo octylmethyl,methylcyclohexyl, phenyl, o-tolyl, p-tolyl, benzyl, B-phenylethyl,p-tolylmethyl, otolylmethyl, 0-(2- chlorotolyl), methoxymethyl,ethoxymethyl, 2-nitroethyl, 2-chloroethyl, 2-bromoethyl, 2-fiuoroethyl,2-cyanoethyl, Z-chloropropyl, 3-chloropropyl, 1,2-dichloropropyl, 2,3-dichloropropyl, 3-bromopropyl, vinyl, allyl, crotyl, pchlorobenzyl,p-bromobenzyl, p-fluorobenzyl, p-nitrobenzyl, p-cyanobenzyl,p-methoxybenzyl, o-carboethoxybenzyl, p-carboethoxybenzyl,p-carbomethoxybenzyl, pentachlorobenzyl, o-methoxybenzyl, 0- orp-ethoxybenzyl,

0- or p-methoxyphenyl, p-chlorophenyl, p-nitrophenyl, pentachlorophenyl,p-carbomethoxyphenyl, p-(N-methylaminophenyl) p- (N-ethylaminophenyl) p-(N,N-dimethylaminophenyl), p (N,N diethylaminophenyl), p-(N-methyl-N-ethylaminophenyl), p-(N-methylaminobenzyl),p-(N-acetylaminophenyl), p-(N-acetylaminobenzyl),pcarbomethoxyaminophenyl), p-(N-carbomethoxyaminobenzyl) 18-(dimethylaminoethyl) B-carboethoxyethyl) p-(N-carbobenzoyaminophenyl),Z-methoxyethyl, 2-ethoxyethyl, 3-methoxypropyl, 3-ethoxypropyl,3-butoxypropyl, 4-methoxybutyl, 4-ethoxybutyl, Z-butoxyethyl, and thosefor R are ethylene, propylene, trimethylene, tetramethylene,pentamethylene, hexamethylene, Z-butenylene, cyclopentylene,cyclohexylene, cyclohexenylene, pphenylene, and residues derived fromp-di(hydroxymethyl) benzene, p-di(hydroxymethyl) cyclohexane, diethyleneglycol and dipropylene glycol.

Although any kind of other amino acids or derivatives thereof consistingof, for example, neutral amino acids, acidic amino acid w-mono estersand Nsubstituted derivatives of basic amino acids, including eitheroptically active or inactive forms, can be used with the glutamic acidqI-ester or esters as the component in the said polymers, it is moredesirable to use glycine, alanine, aaminobutyric acid, valine,norvaline, leucine, isoleucine, norleucine, phenylalanine, O-substitutedserine, O-substituted homoserine, O-substituted threonine,'S-substituted cysteine, cystine, methionine, asparatic,acid-fi-monoester, a-aminoadipic acid-6-monoester, N -substitutedhistidine, proline, N -substituted ornithine, N-substituted lysine, or N-substituted arginine.

Typical examples of polymers are: homopolymers such as poly-y-methylglutamate, poly-'y-ethyl glutamate, polyy-(i-propyl) glutamate,poly-'y-(n-propyl) glutamate, poly-y-(n-butyl) glutamate, poly-y-(i,secor t-butyl) glutamate, poly-y-benzyl glutamate, polyamide polymer ofO O -di('y-glutamyl) ethylene glycol [ethylene glycol di('y-glutamate)],polyamide polymer of O O -di('yglutamyl) trimethylene glycol[trimethylene glycol di('yglutamate)], polyamide polymer of O O-di(v-glutamyl) tetramethylene glycol [tetramehylene glycoldi('y-glutamate)] and polyamide polymer of O O -di(' -glutamyl)hexamethylene glycol [hexamethylene glycol di(-, glutamate) copolymerssuch as copoly-v-methyl glutamate-'y-ethyl glutamate, copoly--y-methylglutamate-'y-(n-propyl) glutamate, copoly-y-methyl glutamate-'y-(i-propyl) glutamate, copoly-v-methyl glutamate-'y-(n-butyl) glutamate,copoly-y-methyl glutamate-y-benzyl glutamate,

.copoly-y-methyl glutamatealanine,

blend polymers such as blend polymers of poly-'y-methyl glutamate andpoly-'y-ethyl glutamate, blend polymers of poly-'y-methyl glutamate andpoly-y-(n-propyl) glutamate, blend polymers of poly-y-methyl glutamateand poly-'y- (i-propyl) glutamate, blend polymers of poly-'y-methylglutamate and poly-y-(n-butyl) glutamate, blend polymers ofpoly-'y-methyl glutamate, poly-'y-ethyl glutamate and poly-y-(n-butyl)glutamate, blend polymers of poly- 'ymethyl glutamate and poly-y-benzylglutamate, blend polymers of poly-'y-methyl glutamate and polyalanine,blend polymers of poly-' -methyl glutamate, poly-'y-ethyl glutamate andpolyalanine, blend polymers of poly-'ymehtyl glutamate andpoly-N-acetyllysine, blend polymers of poly-y-methyl glutamate,polyamide polymers of O O -di('y-glutamyl) ethylene glycol [ethyleneglycol di- ('y-glutamate)] and polyalanine, blend polymers ofpolyv-methyl glutamate, polyamide polymer of O O -di('y glutamyl)trimethylene glycol and poly-'y-butyl glutamate,

blend polymers of poly-'y-methyl glutamate, polyalanine andpolymethionine, blend polymers of poly-y-methyl glutamate andpolymethionine, blend polymers of polyv-methyl glutamate, polyalanineand poly-N-acetyllysine, blend polymers of poly-' -ethyl glutamate andpoly-v-(nbutyl) glutamate, blend polymers of poly-' -ethyl glutamate andpoly-' -(n-propyl) glutamate, blend polymers of poly-'y-ethyl glutamateand poly-'y-(i-propyl) glutamate, blend polymers of poly-'y-ethylglutamate and polyalanine, blend polymers of poly'y-ethyl glutamate andpoly-N acetyllysine, and blend polymers of poly-'y-ethyl glutamate andpolymethionine.

The curing temperature of the urethane resin adhesive used in thepresent invention, which comprises the ester of diisocyanato alkanoicacid as the main ingredient thereof, is preferably from about roomtemperature to 180 C. As the urethane resin adhe'sive of the presentinvention, those having a ratio of the said diisocyanate to polyol ofabout 0.1 to 10.0 in terms of the NCO/ OH ratio is desirable.Particularly advantageous is the ratio of about 0.5 to 3.0.

The following examples are given merely as being illustrative of thepresent invention and accordingly are not to be considered as limiting.The parts noted therein are by weight.

EXAMPLE 1 A urethane resin adhesive of the moisture cured typecomprising 59 parts of the trimethylolpropane adduct of lysinediisocyanate methyl ester (molar ratio 3:1), 5.9 parts of a 10%cellulose acetate butyrate solution in a Cellosolve acetate (trademark,Union Carbide Corporation)-xylene mixture (weight ratio 1:1), 0.6 partof dibutyl tin dilaurate and 120 parts of a Cellosolve acetatexylenemixture (weight ratio 1:1) is prepared. A conventional urethane foamleather comprising cotton suede as the substrate cloth is coated withthe aforesaid urethane resin adhesive so as to form thereon a layer of10 g./m. in terms of solid weight. A greater part of the solvent ispurged off at 40 C. to initiate the curing reaction of the urethaneresin adhesive. The resultant product is then coated with adichloroethane (ethylene dichloride) solution ofpoly-'y-n1ethyl-L-glutamate (polymer content: 10% by weight, molecularweight of polymer: 350,000) to form thereon a layer of 9 g./m. in termsof solid weight, and the solvent is purged off at 40 C. to obtain alustrous synthetic leather, the surface of which is coated Withpoly-'y-methybL-glutamate. Peeling at the face of adhesion of thesynthetic leather is not possible.

EXAMPLE 2 A urethane resin adhesive comprising 45 parts of a mixedsolution (containing by weight of non-volatile substances) of thetrimethylolpropane adduct of lysine diisocyanate methyl ester (molarratio 3:1) and a Cellosolve acetate-xylene mixture (weight ratio 1:1),32 parts of a polyphthalic ester polyether mixture (average OH value:104) containing polypropylene glycol polyether having a molecular weightof 3000 as the main ingredient, and parts of a mixed solvent ofCellosolve acetatexylene (weight ratio 1:1) is prepared.

The surface of a thin plate-like article coated with polyvinyl chloridewhich comprises a textile fabric as the substrate cloth, is coated withthe aforesaid adhesive to form thereon a layer of 20 g./m. in terms ofsolid weight. After purging off the solvent therefrom, the resultantcoated product is adhered with a 0.02 mm. thick film of poly--methyl-L-glutamate and pressed to obtain a lustrous synthetic leather,the surface of which is coated with poly-'y-methyl-Lglutamate. Peelingat the face of adhesion in the thus obtained synthetic leather does notoccur.

EXAMPLE 3 A urethane resin adhesive comprising 19.0 parts of a mixedsolution (containing 80% by weight of non-volatile substances)containing the trimethylolpropane adduct of lysine diisocyanate methylester (molar ratio 3:1) and Cellosolve acetate-xylene (weight ratio1:1), 22.5 parts of Desmophen-1200 (trade name), 1.2 parts ofN-methyldiethanolann'ne, 3.9 parts of cellulose acetate butyrate and50.7 parts of mixed solvent of Cellosolve acetate-xylene (weight ratio1:1) is prepared.

A clean surface of an iron plate is coated with the aforesaid adhesiveso as to form thereon a layer of g./m. in terms of solid weight. Afterpurging off the solvent therefrom, the resultant coated product iscoated with a suspending solution comprising, as the main ingredient, a1,2-dichloroethane (ethylene dichloride) solution of poly-'-methyl-L-glutamate (polymer content: by weight and polymer molecularweight: about 300,000) colored with titanium oxide, to form thereon alayer of 10 g./m. in terms of the polymer weight. The solvent is purgedoff at C. therefrom, and curing of the polyurethane adhesive iscompleted to obtain a coated face having a beautiful white color. Thethus obtained coated face is allowed to stand in a Fade-O-Meter andWeather-O-Meter for 200 hours, respectively. In each case, nodiscoloration is observed.

EXAMPLE 4 A non-woven fabric consisting of of cotton and 50% of rayonstaple is coated with the same urethane adhesive as in Example 2, toform thereon a layer of 30 g./m. in terms of solid weight. When thelayer is semidried, the coated fabric is further coated with a mixedliquid comprising parts of poly-'y-methyl-L-glutamate (molecular weight:about 360,000), 6 parts of di-butyl N-acetyl-glutamate and 904 parts ofethylene dichloride, to form thereon a layer of 80 g./m. The resultantcoated product is dried to obtain a synthetic leather very closelyresembling natural leather, having an improved luster and elongation.Peeling at the face of adhesion in the thusobtained synthetic leather isnot possible.

EXAMPLES 531 The procedure used in the foregoing Example 1 is followedusing the urethane resin adhesive comprising the components indicated inthe following tables and the polymer solution indicated in the followingtables. In each case, the resulting product retains its improvedproperties such as luster, leather-touch (feeling), strong adhesion andnon-yellowing upon prolonged exposure to strong U.V. light.

TABLE Ex. No. Urethane component (parts by weight shown in parentheses)Polymer component 5 LlAdduct 01f (27,56)diisocyanato methyl valerate(83.0), glycerol (10.0) and ethy- Polyw-ethyl-L-glutamate (M.W.300,000).

one g yco 2. Ethylene glycol acetate butyrate (Trade name) (6.0) Do. 3.Dibutyl tin dilaurate (0.3) Do. 4. Triethylamine (0.3) Do. 6.(ll/lighgligellosolve acetate (trademark, Union CarbideCorporation)-xylene D0.

6 1. Adduct oi 2,5-diisocyanato ethyl valerate (80.0), hexanetriol-1,2 6(14.0) and Poly-'y-(n-but l -D- lutamate N. 21

polypropylene glycol (M.W. 1,000) (20.0). y) g W OOOO) 2. Propyleneglycol acetate (10.0) Do. 3. Dibutyl tin dilaurate (0.5) Do. 4.Petroleum benzine Do.

7 1. Adduct of 2,5-diisocyanato n-propyl valerate (85.0) andpentaerythritol (9.0)- Poly-y-(i-propyD-L-glutamate (M.W. 240 000).

2. Ethylene glycol acetate (8.0) Do. 3. Dibutyl tin dilaurate (0.6) Do.4. N-rnethyldiethanolamine (0.6) Do. 5. Ethyl Ccllosolve propionate(trademark, Union Carbide Corporation)- Do.

toluene (1:1) (120).

8 1. .iAddlilit;l3z,g)-dilso0yanato butyl caproate (85.0), glycerol(7.5) and butylene Poly-y-benzyl-Irglutamate (M.W. 470,000).

g yco 2. Silicone XL 520 (trademark) (0.2) Do. 3. Dibutyl tin dilaurate(0.4) Do. 4. N-ethyldicthanolamine (0.5) Do. 5. (Etl;y(l Cellosolveacetate (trademark, Union Carbide Corporation)-xylene Do.

9 1. Adduct of 2,6-diis0cyanato fl-methoxyethyl caproate (75.0) andtrimethylol- Copolymer (M.W. 250,000) of 'y-methyl-D-glutamate a dpropane (10.0). 'y-ethyl-D-glutamate (7:3). 2. Cellulose acetatebutyrate (6.0) Do. 3. Dibutyl tin laurate (0.6). Do. 4.N-rnetl1yldiethanolamine (0.6 Do. 5. Butyl Cellosolve acetate(trademark, U Do.

10 1. Adduct of 2,6-diis0cyanato 'y-chloropropyl caproate (68.0),trimethylolpro- Poly-'y-ehloroeth l-L- lutamate M.W. 2 00 pane (10.0)and polypropylene glycol (M.W. 410) (25.0). y g 2. Ethylene glycolacetate (6.5) Do. 3. Dibutyl tin dilaurate (0.3) Do. 4. MethylCellosolve acetatexylene (1:1) (100) Do.

11 1. Adduct of 2,6-diisocyanato B-bromoethyl valerate (75.0) andtrimethylol- Copolymer (M.W. 270,000) of 'y-methyl-L-glutamate andpropane (11.0). alanine (8:2). 2. Dibutyl tin dilaurate (0.4) Do. 3.Triethylamine (0.4) Do. 4. Ethylene glycol acetate-xylene (1:1) Do.

12 1. Adduct of 2,6-diis0cyanato ethyl caproate (60.0), tlimethylolropane (8.5) Pol -2-methox cth l-L- luta te M.W. 2

butylene glycol-1,3 (2.8) and polypropylene glycol (M.W. 1,000 (33.0). y7 y y g ma soooo) 2. Dibutyl tin dilaurate (0.3) D0. 8. Ethylene glycolacetatcxylene (1:1) (100) Do.

13 1. Adduct of 2,6-diisocyanat0 n-octyl caproate (85.0),pentaerythritol (8.5) and Poly-'y'chlorobenzyl-Dglutamate (M.W. 310000).

hexamethylene glycol-1,6 (16.0). 2. Cellulose acetate butyrate (6.0) Do.3. N-methyldiethanol amine (0.5) Do. 4. Methyl Cellosolve acetatexylene(1:1) (100) Do:

14 1. Adduet of 2,6diisocyanato hexyl caproate (85.0) andtrimethylolpropane Polyamide polymer of O O -di(7-glutamyl) ethylene(12.5 glycol (M.W. 220,000). 2, 3 and 4. Same as in Example 13 Do.

15 1. Adduct of 2,6-diisocyanato n-decyl caproate (80.0) andpentaerythritol (8.0)- Copolymer (M.W. 300,000) of 'y-methyLL-glutamateand 2, 8 and 4. Same as in Example 13 'y-g-propyl) -Irglutamate (8:2).

TABLEContlnued Ex. No. Urethane component (parts by weight shown inparentheses) Polymer component 16 1. Adduct of 2,6-diisocyanato dodecylcaproate (75.0), trimethylol propane Copolymer (M.W. 250,000) of'y-mcthyl-L-glutamate and (11.0) and polypropylene glycol (M.W. 2,000)(30.0). y-butyl-L-glutamate (0:1). 2, 3, 4 and 5. Same as in Example 8Do. 17 1. Adduct of 2,6-diisocyanato stearyl caproate (75.0), glycerol(7.0) and butane- Copolymcr (M.W. 320,000) of 'y-methyl-L-glutamate anddiol 1,4 (7.0). y-methoxyethyl-L-glutamate (7:3). 2, 3, 4 and 5. Same asin Example 8 Do. 18 1. Adduct of 2,6-diisocyanato phenyl caproate(70.0), 1,2,6-hexanetriol (10.0) Copolymer (M.W. 250,000) of'y-ethyl-L-glutamate and and polypropylene glycol (M.W. 2,000) (25.0).y-(n-butyD-Irglutamate (8:2). 2, 3, 4 and 5. Same as in Example 8 Do.19 1. Adduct of 2,6-diisocyanato benzyl caproate (70.0), pentaerythritol(8.0) and Copolymer (M.W. 330,000) of y-methyl-D'glutarnate andpolyethylene glycol (M.W. 1,500) (30.0). 'y-benZyl-D-glutamate (9:1). 2,3, 4 and 5. Same as in Example 8 Do. 20 1. Adduct 012,7-diisocyanatomethyl heptanoate (80.0) and tn'methylol pro- Copolymer (M.W. 260,000)of y-methyl-Irglutarnate and pane (14.0). N e-acetyl-D-lysine (9:1). 2,3, 4 and 5. Same as in Example 5 Do. 21 1. Adduct of 2,8-diisocyanatomethyl caprylate (80.0) and trimethylol propane Copolymer (M.W. 350,000)of y-methyl-D-glutamate anp (14.0 D-methionine (8:2). 2, 3, 4 and 5.Same as in Example 5 D0.

22 1. Adduct 012,7-diisocyanato ethyl heptanoate (80.0) and trimethylolpropane Blend polymer of poly-y-methyl-L-glutamate (M.W (14.0). 420%;00)and poly-y-(n-propyl) glutamate (M.W. 300,000) 2, a, 4 and 5. Same as inExample 5 'Do'. 23 1. Adduct of 2,6-diisocyanato sec-butyl-caproate(80.0) and trimethylol pro- Blend polymer of poly-y-methyl-L-glutamate(M.W. pane (15.0). gOgOO) and poly-y-(t-butyl) Lglutamate (M.W.300,000). 2, 3, 4 and 5. Same as in Example 5 24 1. Adduct of2,4-diisocyanato dimethyl glutarate (60.0), trimethylol propane Blendpolymer of poly-y-methyl-L-glutamate (M.W (10.0) and polypropyleneglycol (M.W. 1,000) (20.0). 23%000) and poly-'y-(n-butyl) glutamate(M.W. 230,000) 2, 3, 4 and 5. Same as in Example 5 Do 25 1. Adduct of2,5-diisocyanato diethyl adipate (60.0), trimethylol propane (10.0)Blend polymer of poly-y-methyl-Lglutamate (MW and polypropylene glycol(M.W. 1,000) (20.0). 260,000) and poly-D-alanine (M.W. 380,000) (7:3).2, 3, 4 and 5. Same as in Example 5 Do. 26 .1 1. Ad duct of2,6-diisocyanato methyl-ethyl pimelate (70.0), trimethylol propane Blendpolymer of pOIy yethyl 'D-glutamate (M.W. 280,000)

(10.0) and polypropylene glycol (M.W. 1,000) (20.0). andpoly-D-methionine (M.W. 400,000) (8:2). 2, 3, 4 and 5. Same as inExample 5 Do. 27 1. Adduct of 2,9-diisocyanato dimethyl sebacate (75.0),trimethylol propane Blend polymer of poly-*y-ethyl-L-glutamate (M.W.320,000)

(10.0) and polypropylene glycol (M.W. 1,000) (20.0). andpoly-ENe-acetyl-L-lysine (M.W. 250,000) (9:1). 2, 3, 4 and 5. Same as inExample 5 Do. 28 1. Adduct of 2,5-diisocyanato dibutyl adipate (70.0)and reaction product of 3 Blend polymer ofpoly-'y-methyl-D-glutamate(M.W

moles propylene oxide with 1 mole trimethylol propane (Dow Chem. 00.320,000 and polybenzyl-Dglutamate (M.W. 380,000) triol designatedVaranol OP 260) (33.0). (9:1). 2, 3, 4 and 5. Same as in Example 5 Do.29 1. Adduct of 2,5-diisocyanato dipropyl adipate (70.0) and trimethylolpropane Blend polymer of poly-'y-methyl-L-glutamate (M.W (10.0).410,000) and polyamide polymer of O O -di (y-Lglutamyl) trimethylencglycol [trimethylene glycol di ('y-L- glutamate)] (M.W. 250,000) (8:2).2, 3, 4 and 5. Same as in Example 8 Do. 30 1. Add)uct of2,6-diisocyanato dihexyl pimelate (70.0) and trimethylol propanePoly-'y-methyl-lrglutamate (M.W. 480,000).

0.0 2, 3, 4 and 5. Same as in Example 8 Do. 31 1. Adduct of2,6-diisocyanato dibenzyl pimelate (70.0) and trimethylol propanePoly-y-methyl-Dglutamate (M.W. 420,000)

0.0 2, 3, 4 and 5. Same as in Example 8 Do.

A comparison between the adhesives of the present invention andadhesives conventionally used for polyolefin films, as in US. Pat.3,198,692 of Bridgeford, has

ester and trimethylolpropane and a polyol consisting essentially ofpropylene glycol (molecular weight: about 3,000)

been carried out in order to show the superiority of the Non-volatilesubstance: 40-50% present adhesives for use with polyglutamic acidcoatings. Solvent: Cellosolve acetate-Xylene The results are shown inthe following description. Viscosity: 10,000- 25,000 cps.

Characteristics of adhesives used: (D) Adhesive (D) (a) Adhesives forpolyolefin (comparison): Principal component: Urethane adduct consist-(A) Bond on 1001 (trade name of Kabushiki mg 9 .lysme lsctyanate methylester a 9 Kaisha Konishi Giske Shohten Japan) consisting essentially ofpolypropylene glycol Principal component: Modified rubber latex(molecular welght: about 400) and tnmeth' Non-volatile substance: 50-53%Nylolpmlie Solvent: Water on-volatile substance. 4050% Viscosity:1,5003000 Solvent: Cellosolve acetate-Xylene-ethane d1- (B) Bond H 12(trade name of Kabushiki Kaisha F 5 00040 00 Konishi Giske Shohten,Japan) vlscoslty 0 Principal component: Synthetic rubber (I) The abovefour adhesives were each coated on a Non-volatile substance: 22-24%separate cotton suede in a proportion of about 2030 g.

Viscosity: 10,000-20,000 cps. (b) The adhesives of the present invention-(C) Adhesive (C) Principal component: Urethane adduct consisting of anadduct of lysine isocyanate methyl (as resin)/m. and a layer ofpoly-'y-methyl-L-glutamate having a molecular Weight of about 200,000Was then applied thereon in a thickness of about 0.02. mm. by aconventional method to form a synthetic leather. When comparing thefinished shape of the poly-' -methyl-L- 1 1 glutamate film on thesurface of the resultant synthetic leather, the degree of softness ofthe respective synthetic leathers was as follows:

Hence, the leather-like materials obtained using conventional polyolefinadhesives are inferior to the synthetic leathers obtained using theadhesives of the present invention.

(II) The following are comparative data obtained by the cantilevermethod at 45 C. (the smaller the figure, the softer the leather):

Cm. Synthetic leather obtained using adhesive (A) 14.5 Base fabric alone9.0 Synthetic leather obtained using adhesive (B 1 15 Synthetic leatherobtained using adhesive (C) 14.0 Synthetic leather obtained usingadhesive (D) 13.5

Or more.

(III) The resulting synthetic leathers were also subjected to anembossing procedure by means of a heated roller (surface temperature:about 100180 C.) to form a pattern on the surface of the leather. In thecase of the leathers obtained by the use of adhesives (A) and (B), thebase fabric was separated from the poly-'y-methyl-L-glutamate layer and,hence, embossing was impossible. On the other hand, in the case of theleathers obtained by the use of adhesives (C) and (D), beautifulpatterns were formed on the surface by embossing, giving excellentsynthetic leather products.

(IV) In addition, the degrees of coloration of the coated productproduced using adhesives (A), (B) and (C), when exposed in aWeather-O-Meter having a xenon light source for 100 hours, were asfollows:

Accordingly, it can be seen that the coated products obtained by the useof the adhesives of the present invention have a low degree ofcoloration and, hence, an excellent resistance to light.

(V) The following results were obtained with tests carried out with aScott-type folding and abrading tester under a load of 1 kg.:

(A) Peeled off and broken at 2,000 times. (B) Peeled off and broken at2,000 times. (C) Peeled off and broken at 5,000 times.

Hence, it can be seen that the synthetic leather composite of thepresent invention has excellent advantages over the products of theprior art with respect to properties such as adhesiveness, gloss, lightresistance, softness and feel, embossability, etc., a well as anenhancement of the elongation thereof, the latter particularly when anacidic amino acid derivative is incorporated into the polyglutamate.

The invention being thus described, it will be obvious that the same maybe varied in many ways. Such variations are not to be regarded as adeparture from the spirit and scope of the invention, and all suchmodifications as would be obvious to one skilled in the art are intendedto be included herein.

What is claimed is:

1. A leather-like composite comprising (1) a substrate coated with (2) apolymer of a glutamic acid-'y-ester or a blend of at least two glutamicacid- -ester Polymers, said glutamic acid-'y-ester having the formula:

COOR4 COOR5OOC (C H2): H2): (C Hz):

CHNH: CHNH: CHNHz O OH O 0 OH O O OH wherein R is a monovalenthydrocarbon group selected from the group consisting of saturated andunsaturated aliphatic hydrocarbon residues having from 1 to 20 carbon12' atoms; saturated and unsaturated cycloaliphatic hydrocarbon residueshaving from 4 to 20 carbon atoms; aryl, alkaryl, aralkyl and aralkenylhydrocarbon residues having from 6 to 20 carbon atoms; and derivativesthereof having at least one substitnent selected from the groupconsisting of chloro, bromo, fluoro, nitro, cyano, alkoxy, carboalkoxy,carboaryloxy, carboalkaryloxy, carboaralkoxy, carboaralkoxy, monoanddialkylated amino, acylated amino, carboalkoxy amino andcarboaralkoxyamino and R is a divalent hydrocarbon group selected fromthe group consisting of the same hydrocarbon residues and derivativesthereof as said R and (3a) an adhesive for the polymer and disposedbetween the polymer and the substrate, said adhesive comprising as theprincipal constituent a compound selected from the group consisting ofdiisocyanate-substituted aliphatic carboxylic acid esters having theformula:

NCO N00 0 R3 -Rz- -C it 1'1 OR. Whrein R is alkyl, alkoxyalkyl,cycloalkyl, aryl, alkaryl or aralkyl or a derivative thereof having atleast one substituent selected from the group consisting of chloro,bromo, fluoro, nitro, alkoxy, carboalkoxy, acylamino, dialkylamino,carboalkoxyamino and carboaralkoxyamino, R is alkylene or alkylidene andR is hydrogen or 0 ll -COY wherein Y is selected from the same group asR or (3b) the reaction product of the diisocyanate compound with apolyol in sufficient quantities to give an NCO/ OH ratio of from 0.1 to10.0.

2. A leather-like composite in accordance with claim 1, wherein saidsubstrate is selected from the group consisting of woven fabrics,knitted fabrics and non-woven fabrics, made of from polyamide fibers,polyester fibers, polyacrylonitrile fibers, polyvinyl chloride fibers,rayon fibers, cotton fibers, silk fibers, wool fibers, linen fibers, orcellulose acetate fibers, and said fabrics having been coated with asynthetic resin comprising polyamide resin, a polyurethane resin, apolyester resin or a polyvinyl chloride resin.

3. A leather-like composite in accordance with claim 1, wherein saidsubstrate is cotton.

4. A leather-like composite in accordance with claim 1, wherein the R Rand Y are selected from the group consisting of methyl, ethyl, n-propyl,i-propyl, n-butyl and isomers thereof, n-pentyl and isomers thereof,nhexyl and isomers thereof, n-heptyl and isomers thereof, n-octyl andisomers thereof, n-decyl and isomers thereof, n-dodecyl(aluryl) andisomers thereof, cetyl, stearyl, oleyl, cyclobutyl, cyclopentyl,cyclohexyl, cycloheptyl, cyclooctyl, cyclobutylmethyl,cyclopentylmethyl, cyclohexylmethyl, cyclooctylmethyl, methylcyclohexyl,phenyl, otolyl, p-tolyl, benzyl, fi-phenylethyl, p-tolylmethyl,otolylmethyl, o-(2-chlorotolyl), methoxymethyl, ethoxymethyl,Z-nitroethyl, 2-chloroethyl, 2-bromoethyl, 2- fiuoroethyl, 2-cyanoethyl,2-chloropropyl, 3-chloropropyl, 1,2-dichloropropyl, 2,3-dichloropropyl,3-bromopropyl, vinyl, allyl, crotyl, p-chlorobenzyl, p-bromobenzyl,pfluorobenzyl, p-nitrobenzyl, p-cyanobenzyl, p-methoxybenzyl,o-carboethoxybenzyl, p-carboethoxybenzyl, pcarbomethoxybenzyl,pentachlorobenzyl, o methoxybenzyl, oand p-ethoxybenzyl, oandp-methoxyphenyl, p-chlorophenyl, p-nitrophenyl, pentachlorophenyl,pcarbomethoxyphenyl, p-(N-methylaminophenyl), p-(N- ethylaminophenyl),p-(N,N-dimethylaminophenyl), p- (N,N-diethylaminophenyl),p-(N-methyl-N-ethylaminophenyl), p-(N-methylaminobenzyl),p-(N-acetylaminophenyl), p-(N-acetylaminobenzyl),p-(N-carbomethoxyaminophenyl), p-(N-carbomethoxyaminobenzyl),fi-(dimethylaminoethyl), ,B-(carboethoxyethyl),p-(N-carbobenzoxyaminophenyl), Z-methoxyethyl, 2-eth0xyethyl, 3-

methoxypropyl, 3-ethoxypropyl, 3-butoxypropyl, 4-methoxybutyl,4-ethoxybutyl and 2-butoxyethyl, the R is selected from the groupconsisting of methylene, ethylene, propylene, trimethylene, butylene,tetramethylene, pentylene, pentamethylene, hexylene and hexamethylene,the R is selected from the group consisting of hydrogen and COOY and theR is selected from the group consisting of ethylene, propylene,butylene, trimethylene, tetramethylene, pentamethylene, hexamethylene,2- butenylene, cyclopentylene, cyclohexylene, cyclohexenylene,p-phenylene and residues derived from p-di(hydroxymethyl)benzene,p-di(hydroxymethyl)cyclohexane, diethylene glycol and dipropyleneglycol.

5. A leather-like composite in accordance with claim 1, wherein thediisocyanate compound is selected from the group consisting of themethyl, ethyl, propyl, butyl, octyl, lauryl and stearyl esters of2,5-diisocyanato valeric acid or 2,6-diisocyanato caproic acid.

6. A leather-like composite in accordance with claim 1, wherein said'y-ester group is selected from the group consisting of methyl, ethyl,n-propyl, i-propyl, n-butyl and isomers thereof, n-pentyl and isomersthereof, n-hexyl and isomers thereof, n-heptyl and isomers thereof,n-octyl and isomers thereof, n-decyl and isomers thereof, n-dodecyl(lauryl) and isomers thereof, cetyl, stearyl, oleyl, cyclobutyl,cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclobutylmethyl,cyclopentylmethyl, cyclohexylmethyl, cyclooctylmethyl, methylcyclohexyl,phenyl, o-tolyl, ptolyl, benzyl, fi-phenylethyl, p-tolylmethyl,o-tolylmethyl, o-(2-chlorotolyl), methoxymethyl, ethoxymethyl, 2-nitroethyl, 2-chloroethyl, 2-bromoethyl, Z-fluoroethyl, 2- cyanoethyl,2-chloropropyl, 3-chloropropyl, 1,2-dichloropropyl, 2,3-dichloropropyl,3-bromopropyl, vinyl, allyl, crotyl, p-chlorobenzyl, p-bromobenzyl,p-fluorobenzyl, pnitrobenzyl, p -cyanobenzyl, p-methoxybenzyl,o-carboethoxybenzyl, p-carboethoxybenzyl, p carbomethoxybenzyl,pentachlorobenzyl, o-methoxybenzyl, oand pethoxybenzyl, oandp-methoxyphenyl, pchlorophenyl, p-nitrophenyl, pentachlorophenyl,p-carbomethoxyphenyl, p- (N-methylaminophenyl) p- (N-ethylaminophenyl)p- (N,N-dimethylaminophenyl), p (N,N diethylaminophenyl), p-(N-methyl Nethylaminophenyl), p-(N- methylaminobenzyl), p-(N-acetylaminophenyl) p-(N- acetylaminobenzyl), p (N-carbomethoxyaminophenyl),p-(N-carbomethoxyaminobenzyl), B (dimethylaminoethyl),fl(carboethoxyethyl), p-(N-carbobenzoxyaminophenyl), Z-methoxyethyl,Z-ethoxyethyl, 3-methoxypropyl, 3-ethoxypropyl, 3-butoxypropyl,4-methoxybutyl, 4- ethoxybutyl, 2-butoxyethyl, ethylene, propylene,butylene, trimethylene, tetramethylene, pentamethylene, hexamethylene,Z-butenylene, cyclopentylene, cyclohexylene, cyclohexenylene,p-phenylene and residues derived from p di(hydroxymethyl)benzene, pdi(hydroxymethyl) cyclohexane, diethylene glycol and dipropylene glycol.

7. A leather-like composite in accordance with claim 1, wherein saidpolymer comprises a copolymer of said glutamic acid-' -ester and amoiety of a neutral amino acid, an w-monoester of an acidic amino acid,an N -substituted basic amino acid or a derivative thereof.

8. A leather-like composite in accordance with claim 7, wherein themoiety copolymerized with said glutamic acid-'y-ester is selected fromthe group consisting of glycine, alanine, a-aminobutyric acid, valine,norvaline, leucine, isoleucine, norleucine, phenylalanine, O-substitutedserine, O-substituted homoserine, O-substituted threonine, S-substitutedcysteine, cystine, methionine, aspartic acid-fi-monoester, a-aminoadipicacid-fi-monoester, N -substituted histidine, proline, N"-substitutedornithine, N -substituted lysine and N substituted arginine.

9. A leather-like composite in accordance with claim 1, wherein saidpolymer is selected from the group consisting of poly-'-methyl-glutamate, poly-'y-ethyl-glutamate, poly-'y- (i-propyl)glutamate, poly-'y- (n-propyl) -glutam ate,

14 poly-'y-(n-butyl)-glutamate, poly-'y-(i-, secand t-butyl)- glutamate,poly-'y-benzyl-glutamate, polyamide polymers of O ,O-di-('y-glutamyl)-ethylene glycol, copoly-' -methyl glutamate-'y-ethylglutamate, copoly-'y-methyl glutamatey-(n-propyl) glutamate,copoly-'y-methyl glutamate-y- (n-butyl) glutamate, copoly 'y methylglutamate-ybenzyl glutamate, copoly-'y-methyl glutamate-alanine,copoly-'y-methyl glutamate-N -acetyllysine, copoly-'y-methylglutamate-methionine, copoly-'y-methyl glutamate-'y-ethylglutamate-'y-(n-propyl) glutamate, copoly-'y-methyl glutamate-v-ethylglutamate-v-(i-propyl) glutamate, copolyv-methyl glutamate-v-ethylglutamate-'y-butyl glutamate, copoly-'y-methylglutamate-alanine-methionine, copolymethyl glutamate-O ,O-di(v-glutamyl) ethylene glycol- 'y-(i-propyl) glutamate, blend polymersof poly-' -methyl glutamate and poly-'y-ethyl glutamate, blend polymersof poly-'y-methyl glutamate and poly-'y-(n-propyl) glutamate, blendpolymers of poly-'y-methyl glutamate and poly-'y-(i-propyl) glutamate,blend polymers of poly-vmethyl glutamate and poly-y-(n-butyl) glutamate,blend polymers of poly-v-methyl glutamate, poly-y-ethyl glutamate andpoly-'y-(n-butyl) glutamate, blend polymers of poly-y-methyl glutamateand poly-'y-benzyl glutamate, blend polymers of poly-'y-methyl glutamateand polyalanine, blend polymers of poly-' -methyl glutamate,poly-'yethyl glutamate and polyalanine, blend polymers of polyv-methylglutamate and poly-N -acetyllysine, blend polymers of poly-'y-methylglutamate, polyamide polymers of O ,O -di('y-glutamyl) ethylene glycoland polyalanine, blend polymers of poly-'y-methyl glutamate, polyamidepolymers of O ,O -di('y-glutamyl) trimethylene glycol and poly-'y-butylglutamate, blend polymers of poly-'ymethyl glutamate, polyalanine andpolymethionine, blend polymers of poly-'y-methyl glutamate andpolymethionine, blend polymers of poly-'y-methyl glutamate, polyalanineand poly-N -acetyllysine, blend polymers of poly-' -ethyl glutamate andpoly-'y-(n-butyl) glutamate, blend polymers of poly-' -ethyl glutamateand poly-' -(n-butyl) glutamate, blend polymers of poly-'y-ethylglutamate and poly-' -(n-propyl) glutamate, blend polymers ofpoly-'yethyl glutamate and poly-'y-(i-propyl) glutamate, blend polymersof poly-' -ethyl glutamate and polyalanine, blend polymers ofpoly-v-ethyl glutamate and poly-N- acetyllysine and blend polymers ofpoly-'y-ethyl glutamate and polymethionine.

10. A leather-like composite in accordance with claim 1, wherein saidpolymer contains a plasticizer therefor.

11. A leather-like composite in accordance with claim 10, wherein saidplasticizer is a diester of an acidic amino acid or an N-substitutedderivative thereof.

12. A leather-like composite in accordance with claim 1, wherein saidcopolymer contains a color-producing material.

13. A leather-like composite in accordance with claim 1, wherein thesubstrate is a woven or nonwoven fabric.

14. A leather-like composite in accordance with claim 1, wherein saidadhesive includes a material selected from the group consisting ofdiols, polyols, polyol polyesters and acrylic-modified polyols.

15. A leather-like composite in accordance with claim 1, wherein saidadhesive includes a polyol, the ratio of the polyol to the diisocyanatecompound being about 0.5 to 3.0.

16. A leather-like composite comprising (1) a cotton suede substratecoated with (2) a polymer of a glutamic acid-'y-ester or a blend of atleast two glutamic acid-'yester polymers and (3a) an adhesive for thepolymer and disposed between the polymer and the substrate, saidadhesive comprising as the principal constituent adiisocyanato-substituted aliphatic carboxylic acid ester or (3b) thereaction product of the diisocyanate compound with a polyol insuificient quantities to give an NCO/ OH ratio of from 0.1 to 10.0.

17. A leather-like composite in accordance with claim 15 16, whereinsaid adhesive is a diisocyanate compound having the formula:

N N00 0 R -R1( JC Iii: \O R1 wherein R is an organic moiety, R isalkylene or alkylidene and R is hydrogen or Y being an organic moiety.

18. A leather-like composite in accordance with claim 17, wherein R andY are alkyl, alkoxyalkyl, cycloalkyl, aryl, alkaryl or aralkyl or aderivative thereof having at least one substituent selected from thegroup consisting of chloro, bromo, fluoro, nitro, alkoXy, carboal'koxy,acylamino, dial'kylamino, carboalkoxyamino and carboaralkoxyamino.

19. A leather-like composite in accordance with claim 18, wherein theNCO/OH ratio in said adhesive is about 0.5 to 3.0.

16 20. A leather-like composite in accordance with claim 17, wherein thecuring temperature of said diisocyanate compound is about roomtemperature to about 180 C.

References Cited UNITED STATES PATENTS 3,582,397 6/1971 S'hibata 26078 A3,537,871 11/1970 Kaneko 11776 T 3,582,442 6/1971 Kaneko 16l-1903,356,650 12/1967 McElroy 1611'90 3,422,165 1/1'969 'Brotherton et al l6l190 3,371,069 2/1968 Miyamao et a1. 2 607'8 A 3,475,386 10/1969 Meigset a1. 260-78 A WILLIAM A. POWELL, Primary Examiner G. W. MOXON II,Assistant Examiner US. Cl. X.R.

117-76 T, A, 161 KP, 161 UN; 161-170, 190, 227, Dig. 2

